Polymerizable liquid crystal composition and optical anisotropical body thereof

ABSTRACT

A polymerizable liquid crystal composition is presented which can form a polymer that allows formation of a uniform homeotropic alignment even without forming an alignment film on the supporting substrate and has excellent chemical strengths such as heat resistance and solvent resistance. The polymerizable liquid crystal composition includes at least one type of polyfunctional polymerizable liquid crystal compound and a cardo-type fluorene monomer, wherein based on a total amount of the polyfunctional polymerizable liquid crystal compound, a content of a monofunctional polymerizable liquid compound is less than 5.0% by weight.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of and claims thepriority benefit of a prior application Ser. No. 15/183,802, filed onJun. 16, 2016, now allowed as U.S. Pat. No. 10,155,904. The priorapplication Ser. No. 15/183,802 claims the priority benefit of Japanapplication serial no. 2015-122275, filed on Jun. 17, 2015. The entiretyof each of the above-mentioned patent application is hereby incorporatedby reference herein and made a part of this specification.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention generally relates to a polymerizable liquidcrystal composition and an optical anisotropical body obtainedtherefrom, and further relates to an optical compensation element and anoptical element that uses the optical anisotropical body.

2. Description of Related Art

Polymerizable liquid crystal compounds having a liquid crystal phase canbe used to obtain a polymer having optical compensation functionsthrough polymerization. That is, the alignment of the liquid crystalcompound is fixed through polymerization. In order to take advantages ofthe features of such polymers, a variety of polymerizable liquid crystalcompounds have been developed.

However, a single polymerizable liquid crystal compound cannot meetsufficient functionality. In patent documents 1-4, compositions wereprepared from a variety of polymerizable liquid crystal compounds,wherein the composition was polymerized.

For polymers having homeotropic alignment, the direction of the opticalaxis is in the n_(z) direction, and since the refractive index in theoptical axis direction is larger than the refractive index in anorthogonal direction, the refractive index ellipsoid is classified aspositive C-plate. In non-patent document 1 and non-patent documents 2, 5and 6, for optical compensation of the liquid crystal mode where theliquid crystals are horizontally aligned during black display orso-called IPS (In-Plane Switching) mode, and the like, for example, inorder to improve the viewing angle characteristics of the polarizers,the positive C-plate is combined with films having other opticalfunctions.

In the above applications, there are situations where the polymerizableliquid crystal material is laminated onto a supporting substrate such asglass substrate or plastic substrate. Examples of the materials used asthe plastic substrate are such as polymers of TAC (triacetyl cellulose),polycarbonate, PET, acrylic resins and cycloolefin resins.

For making the polymerizable liquid crystal compound to have homeotropicalignment, patent document 7 discloses that when the supportingsubstrate is a glass substrate, the structure of the polymerizableliquid crystal compound is selected for expressing smectic phase. Formaking the polymerizable liquid crystal compound to have homeotropicalignment, patent document 8 discloses that lecithin is applied on theglass substrate as a vertical alignment film. In patent documents 1 and9, an alignment film is formed on the plastic supporting substrate.

In patent documents 10, 11 and 12, even without forming an alignmentfilm on the supporting substrate, methods for preparing a uniformpolymerizable liquid crystal compound having homeotropic alignment aredisclosed. For instance, patent document 12 discloses a polymerizableliquid crystal compound having a monofunctional polymerizable functionalgroup. However, for the optical anisotropical body obtained bypolymerizing the compositions described in patent documents 10, 11 and12, the anisotropy is lowered due to heat and deterioration issignificant due to the contact with solvents.

PATENT DOCUMENTS

-   Patent Document 1: Japanese Laid Open Publication No. H10-319408-   Patent Document 2: Japanese Laid Open Publication No. 2004-198478-   Patent Document 3: Japanese Laid Open Publication No. 2002-243942-   Patent Document 4: Japanese Laid Open Publication No. 2005-196221-   Patent Document 5: PCT International Publication No. 2005/38517-   Patent Document 6: US Patent Application Publication No. 2006/182900-   Patent Document 7: Japanese Laid Open Publication No. 2000-514202-   Patent Document 8: Japanese Laid Open Publication No. H07-294735-   Patent Document 9: PCT International Publication No. 2004/72699-   Patent Document 10: Japanese Laid Open Publication No. 2006-126757-   Patent Document 11: Japanese Laid Open Publication No. 2008-266550-   Patent Document 12: Japanese Laid Open Publication No. 2008-266632

NON-PATENT DOCUMENTS

-   Non-Patent Document 1: M. S. Park et al., IDW '04 FMCS-4-   Non-Patent Document 2: M. Nakata et al., SID '06 P-58

SUMMARY OF THE INVENTION Problems to be Solved

The present invention provides a polymerizable liquid crystalcomposition which can form a polymer that allows formation of a uniformhomeotropic alignment even without forming an alignment film on thesupporting substrate and has excellent chemical strengths such as heatresistance and solvent resistance. Additionally, the present inventionfurther provides an alignment controlled liquid crystal layer obtainedby the polymerizable liquid crystal composition, an opticalanisotropical body formed by polymerizing the polymerizable liquidcrystal composition and an optical compensation element that uses theoptical anisotropical body.

Means for Solving the Problem

To accomplish the present invention, the inventors have used acardo-type fluorene monomer as a component of the polymerizable liquidcrystal composition, and in the case where the supporting substrate is aglass substrate or a plastic film, even without using a verticalalignment film having long-chain alkyl groups or inorganic materials forsurface treatment, the polymerizable liquid crystal compound may beeffective in controlling uniform homeotropic alignment, and further,with the combined usage of a specific polymerizable liquid crystalcompound, and the composition contains no monofunctional polymerizableliquid crystal compound or contains the monofunctional polymerizableliquid crystal compound in trace amounts, a polymer having significantlyimproved chemical strengths such as heat resistance and solventresistance can be produced. Such cardo-type fluorene monomer has atleast one or more (meth)acryloyloxy group and is polymerizable in thesame manner as the polymerizable liquid crystal compound. The polymerobtained from the polymerizable liquid crystal composition shows auniform homeotropic alignment, which can achieve the same effect wherethe polymerizable liquid crystal composition is coated on the supportingsubstrate through mechanical surface treatment such as rubbing, orthrough chemical surface treatment. The polymerizable liquid crystalcomposition is represented by the following [1] items.

[Item 1] A polymerizable liquid crystal composition, comprising: apolyfunctional polymerizable liquid crystal compound and a cardo-typefluorene monomer, wherein based on a total amount of the polyfunctionalpolymerizable liquid crystal compound, a content of a monofunctionalpolymerizable liquid compound is less than 5.0% by weight.

[Item 2] The polymerizable liquid crystal composition according to [item1], wherein the cardo-type fluorene monomer is at least one compoundselected from the group of compounds represented by formula (A-1) to(A-6):

wherein, in formula (A-1), L^(1a) and L^(1b) independently representalkyl having 1 to 4 carbons, R^(1a) and R^(1b) independently representalkylene having 2 to 4 carbons, Z³¹ independently represents hydrogen ormethyl, k1 and k2 independently represent an integer from 0 to 4, m31and n31 independently represent an integer from 0 to 6;

in formula (A-2), Z³² independently represents hydrogen or methyl, m32and n32 independently represent an integer from 1 to 3, L^(2a) andL^(2b) independently represent alkyl having 1 to 6 carbon, phenyl orfluorine, j1 and j2 independently represent an integer from 0 to 4;

in formula (A-3), Z³³ independently represents hydrogen or methyl,R^(3a) and R^(3b) independently represent hydrogen, methyl or ethyl, m33and n33 independently represent an integer from 0 to 3;

in formula (A-4), Z³⁴ represents hydrogen or methyl, R^(4a) and R^(4b)independently represent hydrogen or alkyl having 1 to 6 carbons, m34 andn34 independently represent an integer from 0 to 10;

in formula (A-5), Z³⁵ independently represents hydrogen or methyl;

in formula (A-6), Z³⁶ independently represents hydrogen or methyl,R^(5a) and R^(5b) independently represent hydrogen or alkyl having 1 to6 carbons, L^(2a) and L^(2b) independently represent alkyl having 1 to 6carbons, phenyl or fluorine, j1 and j2 independently represent aninteger from 0 to 4, m35 and n35 independently represent an integer from1 to 3, m36 and n36 independently represent an integer from 1 to 3.

[Item 3] The polymerizable liquid crystal composition according to [item2], wherein the cardo-type fluorene monomer is at least one compoundselected from the group of compounds represented by formula (A-1),formula (A-2), formula (A-3), formula (A-5) and formula (A-6).

[Item 4] The polymerizable liquid crystal composition according to anyone of [item 1] to [item 3], wherein a polymerizable functional group ofthe polyfunctional polymerizable liquid crystal compound is a(meth)acryloxy group.

[Item 5] The polymerizable liquid crystal composition according to anyone of [item 1] to [item 4], wherein the polyfunctional polymerizableliquid crystal compound is at least one compound selected from the groupof compounds represented by formula (M-1) and formula (M-2):

wherein, in formula (M-1) and formula (M-2), A^(M) independentlyrepresents a divalent group selected from 1,4-phenylene,1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl,1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl or fluorene-2,7-diyl, whereinin the divalent group, at least one hydrogen may be substituted byfluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl,difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxyhaving 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkanoylhaving 1 to 5 carbons,

Z^(M) independently represents a single bond, —OCH₂—, —CH₂O—, —COO—,—OCO—, —COS—, —SCO—, —OCOO—, —CONH—, —NHCO—, —CF₂O—, —OCF₂—, —CH₂CH₂—,—CF₂CF₂—, —CH═CHCOO—, —OCOCH═CH—, —CH₂CH₂COO—, —OCOCH₂CH₂—, —CH═CH—,—N═CH—, —CH═N—, —N═CCH₃—, —CCH₃═N—, —N═N— or —C≡C—,

q represents an integer from 1 to 4,

c and d independently represents an integer from 0 to 3, wherein1≤c+d≤4,

a independently represents an integer from 0 to 20,

R^(M) independently represent hydrogen or methyl,

Y^(M) independently represent a single bond, —O—, —COO—, —OCO— or—OCOO—,

Q represents a single bond, —O—, —COO—, —OCO— or —OCOO—.

[Item 6] The polymerizable liquid crystal composition according to anyone of [item 1] to [item 5], wherein based on a total amount of thepolymerizable liquid crystal composition, a content of thepolyfunctional polymerizable liquid crystal compound is from 3% byweight to 60% by weight.

[Item 7] The polymerizable liquid crystal composition according to anyone of [item 1] to [item 6], wherein based on a total amount of thepolymerizable liquid crystal composition, a content of the cardo-typefluorene monomer is from 0.01% by weight to 15% by weight.

[Item 8] A polymerizable liquid crystal layer, obtained by applying thepolymerizable liquid crystal composition according to any one of [item1] to [item 7] directly onto a support substrate.

[Item 9] The polymerizable liquid crystal layer according to [item 8],wherein the support substrate is a glass substrate.

[Item 10] The polymerizable liquid crystal layer according to [item 8],wherein the support substrate is a glass substrate coated with plasticthin film or a plastic substrate made of plastic film.

[Item 11] The polymerizable liquid crystal layer according to [item 8],wherein the support substrate is a glass substrate coated with plasticthin film by rubbing treatment, corona treatment or plasma treatment onthe surface, or the support substrate is a plastic substrate made ofplastic film with rubbing treatment, corona treatment or plasmatreatment on the surface.

[Item 12] The polymerizable liquid crystal layer according to [item 10]or [item 11], wherein a plastic of the plastic thin film and the plasticfilm is at least one selected from polyimide, polyamide-imide,polyamide, polyether-imide, polyether ether ketone, polyether ketone,polyketone sulfide, polyether sulfone, polysulfone, polyphenylenesulfide, polyphenylene oxide, polyethylene terephthalate, polybutyleneterephthalate, polyethylene naphthalate, polyacetal, polycarbonate,polyarylate, acrylic resins, polyvinyl alcohol, polypropylene,cellulose, triacetyl cellulose, partially saponified product oftriacetyl cellulose, epoxy resins, phenolic resins and cycloolefinresins.

[Item 13] The polymerizable liquid crystal layer according to [item 10]or [item 11], wherein a plastic of the plastic thin film and the plasticfilm is at least one selected from polyimide, polyvinyl alcohol,triacetyl cellulose, partially saponified product of triacetylcellulose, acrylic resins, and cycloolefin resins.

[Item 14] The polymerizable liquid crystal layer according to any one of[item 8] to [item 13], wherein an alignment state of the liquid crystalof the polymerizable liquid crystal composition is homeotropicalignment.

[Item 15] A liquid crystal film, obtained by polymerizing thepolymerizable liquid crystal layer according to any one of [item 8] to[item 13].

[Item 16] An optical compensation element, comprising the liquid crystalfilm of [item 15].

[Item 17] An optical element, comprising the liquid crystal film of[item 15] and a polarizer.

Effects of the Invention

By adding a cardo-type fluorene monomer to a specific polymerizableliquid crystal compound, even without using a vertical alignment filmhaving long-chain alkyl groups or inorganic materials for surfacetreatment, a uniform homeotropic alignment can be obtained. Furthermore,for the optical anisotropical body obtained from the polymerizableliquid crystal composition of the present invention, since it does notcontain the monofunctional polymerizable liquid crystal compound used inthe production of the conventional optical anisotropical body, or isonly contained in trace amounts, therefore, it may be useful inproviding good chemical strength and improved reliability.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide a furtherunderstanding of the invention, and are incorporated in and constitute apart of this specification. The drawings illustrate embodiments of theinvention and, together with the description, serve to explain theprinciples of the invention.

FIG. 1 shows the retardation measurement results of an opticalanisotropical body obtained in Example 1.

FIG. 2 shows a content of compound (M-3-2) versus heat resistance of theoptical anisotropical body corresponding to the compositions 36-40 inExample 32. X-axis of FIG. 2 shows the percentage of a content ofcompound(M-3-2), based on a total amount of the polyfunctionalpolymerizable liquid crystal compound. Y-axis of FIG. 2 shows heatresistance of the optical anisotropical body.

FIG. 3 shows a content of compound (M-3-1) versus heat resistance of theoptical anisotropical body corresponding to the compositions 31-35 inExample 31. X-axis of FIG. 3 shows the percentage of a content ofcompound(M-3-1), based on a total amount of the polyfunctionalpolymerizable liquid crystal compound. Y-axis of FIG. 3 shows heatresistance of the optical anisotropical body.

DESCRIPTION OF THE EMBODIMENTS

Regarding the term “polymerizable”, this refers to the ability ofpolymerization through means such as light, heat or catalyst, such thatcompounds with larger molecular weights can be provided.

Regarding the term “polymerizable functional group”, this refers to afunctional group that can be polymerized.

Regarding the term “monofunctional”, this refers to the case where onlyone polymerizable functional group exists in one molecule.

Regarding the term “polyfunctional”, this refers to the case wheremultiple polymerizable functional groups exist in one molecule.

Regarding the term “liquid crystallinity”, this refers to being able tobecome the compounds have a liquid crystal phase or the compounds do nothave a liquid crystal phase but is useful as a component in the liquidcrystal composition.

Regarding the term “liquid crystal compound”, this is a generic termreferring to the compounds have a liquid crystal phase or the compoundsdo not have a liquid crystal phase but is useful as a component in theliquid crystal composition.

Regarding the term “polymerizable liquid crystal compound”, this refersto a liquid crystal compound that can be polymerized.

Regarding the term “liquid crystal phase” this is a generic termreferring to nematic phase, smectic phase and cholesteric phase.

Regarding the term “liquid crystal lower limit temperature”, this refersto the temperature where the liquid crystal phase is transferred intocrystals as determined by the experimental methods provided in thepresent disclosure.

Regarding the term “(meth)acrylic”, this is a generic term referring toacrylic and methacrylic.

Regarding the term “(meth)acrylic acid”, this is a generic termreferring to acrylic acid and methacrylic acid.

Regarding the term “(meth)acrylate”, this is a generic term referring toacrylate and methacrylate.

Regarding the term “liquid crystal thin film”, this refers to a thinfilm made from the polymerizable liquid crystal composition.

Regarding the term “liquid crystal film”, this refers to a film-likeoptical anisotropical body formed from the polymerizable liquid crystalcomposition.

Regarding the term “chemical strength”, this refers to the smallness ofchange in the mechanical properties and optical properties of thetarget, before and after high temperature load, or before and afterimmersion in solvent.

The compounds represented by formula (1) may be referred to as compound(1). The compounds represented by other formulas may also be referredusing the same simplified method above.

In explaining the structures of compounds, the term “at least one” isnot only used to describe at least one position, but also tends to meanthat the number is at least one. For example, “at least one of A may besubstituted by B, C or D” tends to mean that at least one of A may besubstituted by B, at least one of A may be substituted by C and at leastone of A may be substituted by D, and further includes the case where aplurality of A may be substituted by at least two of B˜D.

As for chemical formulas, as in the case shown below, the straight linefrom A to B tends to mean a bonding, wherein if hydrogen in A issubstituted by group B, this tends to mean a replacement at anyposition. X indicates the number of the substituted group B. In the casewhere X is 0, this tends to mean that B does not exist, or that it isnot substituted.

[Polymerizable Liquid Crystal Composition]

The polymerizable liquid crystal composition of the present inventionincludes at least one type of polyfunctional polymerizable liquidcrystal compound and a cardo-type fluorene monomer, and based on a totalamount of the polyfunctional polymerizable liquid crystal compound, acontent of a monofunctional polymerizable liquid compound is less than5.0% by weight.

[1. Cardo-Type Fluorene Monomer]

Cardo-type fluorene monomers are polymerizable compounds where afluorene backbone is substituted with two phenyl groups at the9-position. Furthermore, such compounds have an effect of homeotropicalignment for liquid crystal compounds.

Cardo-type fluorene monomers are compounds including the followingformula (A-1) to formula (A-6):

wherein, in formula (A-1), L^(1a) and L^(1b) independently representalkyl having 1 to 4 carbons, R^(1a) and R^(1b) independently representalkylene having 2 to 4 carbons, Z³¹ independently represents hydrogen ormethyl, k1 and k2 independently represent an integer from 0 to 4, m31and n31 independently represent an integer from 0 to 6;

in formula (A-2), Z³² independently represents hydrogen or methyl, m32and n32 independently represent an integer from 1 to 3, L^(2a) andL^(2b) independently represent alkyl having 1 to 6 carbon, phenyl orfluorine, j1 and j2 independently represent an integer from 0 to 4;

in formula (A-3), Z³³ independently represents hydrogen or methyl,R^(3a) and R^(3b) independently represent hydrogen, methyl or ethylgroup, m33 and n33 independently represent an integer from 0 to 3;

in formula (A-4), Z³⁴ represents hydrogen or methyl, R^(4a) and R^(4b)independently represent hydrogen or alkyl having 1 to 6 carbons, m34 andn34 independently represent an integer from 0 to 10;

in formula (A-5), Z³⁵ independently represents hydrogen or methyl;

in formula (A-6), Z³⁶ independently represents hydrogen or methyl,R^(5a) and R^(5b) independently represent hydrogen or alkyl having 1 to6 carbons, L^(2a) and L^(2b) independently represent alkyl having 1 to 6carbons, phenyl or fluorine, j1 and j2 independently represent aninteger from 0 to 4, m35 and n35 independently represent an integer from1 to 3, m36 and n36 independently represent an integer from 1 to 3.

In formula (A-1), from the viewpoint of heat resistance, preferably,R^(1a) and R^(1b) individually represents an alkylene having 2 to 4carbons, Z³¹ independently represents hydrogen or methyl, k1 and k2 arerespectively 0, and preferably, m31 and n31 independently represent aninteger from 0 to 4.

In formula (A-2), from the viewpoint of heat resistance, Z³²independently represents hydrogen or methyl, preferably, m32 and n32independently represent an integer of 1 or 2, and preferably, j1 and j2are respectively 0.

In formula (A-3), from the viewpoint of heat resistance, Z³³independently represents hydrogen or methyl, preferably, R^(3a) andR^(3b) independently represent hydrogen or methyl, and preferably, m33and n33 independently represent an integer from 0 to 2.

In formula (A-4), from the viewpoint of heat resistance, Z³⁴ representshydrogen or methyl, preferably, R^(4a) and R^(4b) independentlyrepresent hydrogen or methyl, and preferably, m34 and n34 independentlyrepresent an integer from 0 to 2.

In formula (A-6), from the viewpoint of heat resistance, Z³⁶independently represents hydrogen or methyl, preferably, R^(5a) andR^(5b) independently represent hydrogen or methyl, j1 and j2 arerespectively 0, preferably, m35 and n35 independently represent aninteger from 1 to 2, and preferably, m36 and n36 independently representan integer from 1 to 2.

The cardo-type fluorene monomer contained in the polymerizable liquidcrystal composition of the present invention may be a single type, or bein multiple combinations.

Cardo-type fluorene monomers represented by formula (A-1), formula(A-2), formula (A-3), formula (A-5) and formula (A-6) are preferablyused from the viewpoint of heat resistance and solubility. In addition,when the cardo-type fluorene monomers are used in multiple combinations,for example, the combinations of (A-1) and (A-6), (A-2) and (A-3), (A-2)and (A-4), (A-2) and (A-6) or (A-3) and (A-6) are preferable from theview point of heat resistance and solubility.

By considering the solubility, based on a total amount of thepolymerizable liquid crystal composition, a content of the cardo-typefluorene monomer in the polymerizable liquid crystal composition ispreferably from 0.01% by weight to 15% by weight, and more preferably0.03% by weight to 10% by weight.

By considering the solubility, based on a total amount of thepolyfunctional polymerizable liquid crystal compound, a content of thecardo-type fluorene monomer is preferably 1% by weight to 25% by weight,and more preferably 5% by weight to 20% by weight.

[2. Polymerizable Liquid Crystal Compound]

The main polymerizable liquid crystal compound used in the presentinvention is polyfunctional. The polymer product obtained from thecomposition containing the polyfunctional polymerizable liquid crystalcompound can have a three dimensional structure. As a result, incomparison to a polymer product obtained from the composition notcontaining polyfunctional polymerizable liquid crystal compounds, butonly contains monofunctional polymerizable liquid crystal compounds, thepolymers of the present invention will have an improved hardness, andexcellent heat resistance and solvent resistance, and the like.

The aforementioned polymerizable functional groups are for example,carboxyl group, (meth)acrylic group, epoxy group, thiol-epoxy group,mercapto group, isocyanate group, isothiocyanate group, oxetane group,thietanyl group, aziridinyl group, pyrrole group, vinyl group, allylgroup, fumarate group, cinnamoyl group, oxazoline group, hydroxyl group,alkoxysilyl group and amino group, and the like. In the case of making anormally used light curing film, in order to increase the hardness, andincrease the solubility in the solvents of the polymerizable compoundand improve the handling, the polymerizable functional group ispreferably an acrylic group or a methacrylic group.

The polyfunctional polymerizable liquid crystal compound are compoundsthat are represented by formula (M-1) and (M-2).

wherein, in formula (M-1) and formula (M-2),

A^(M) independently represents a divalent group selected from1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene,pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl orfluorene-2,7-diyl, wherein in the divalent group, at least one hydrogenmay be substituted by fluorine, chlorine, cyano, hydroxy, formyl,trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5carbons or alkanoyl having 1 to 5 carbons,

Z^(M) independently represents a single bond, —OCH₂—, —CH₂O—, —COO—,—OCO—, —COS—, —SCO—, —OCOO—, —CONH—, —NHCO—, —CF₂O—, —OCF₂—, —CH₂CH₂—,—CF₂CF₂—, —CH═CHCOO—, —OCOCH═CH—, —CH₂CH₂COO—, —OCOCH₂CH₂—, —CH═CH—,—N═CH—, —CH═N—, —N═CCH₃—, —CCH₃═N—, —N═N— or —C≡C—,

q represents an integer from 1 to 4,

c and d independently represents an integer from 0 to 3, wherein1≤c+d≤4,

a represents an integer from 0 to 20,

R^(M) independently represent hydrogen or methyl,

Y^(M) independently represent a single bond, —O—, —COO—, —OCO— or —COO—,

Q represents a single bond, —O—, —COO—, —OCO— or —OCOO—.

In the case where q, c, or d is 2 or more, then A^(M) and Z^(M) may bedifferent in each repeat.

The compounds represented by formula (M-1) are illustrated below.

In formula (M-1-1) to (M-1-31), R^(M) independently represents hydrogenor methyl, a independently represents an integer from 1 to 12.

The compounds represented by formula (M-2) are illustrated below.

In formula (M-2-1) to (M-2-11), R^(M) independently represents hydrogenor methyl, a independently represent an integer from 1 to 12.

In the compounds represented by formula (M-1) and (M-2) above, from theviewpoint of heat resistance and solubility, the compounds preferablyused are, (M-1-1), (M-1-2), (M-1-7), (M-1-8), (M-1-9), (M-1-10),(M-1-12), (M-1-15), (M-1-22), (M-1-23), (M-1-24), (M-1-25), (M-1-29),(M-1-30), (M-2-1), (M-2-4), (M-2-7), (M-2-10), (M-2-11), and morepreferably (M-1-1) and (M-1-2), (M-1-3), (M-1-7), (M-1-8), (M-1-9),(M-1-10), (M-1-12), (M-1-22), (M-1-23), (M-1-24), (M-1-25), (M-1-29),(M-1-30), (M-2-1), (M-2-10), (M-2-11). The above compounds may be usedalone or in multiple combinations.

In the liquid crystal composition, from the viewpoint of solubility,based on a total amount of the polymerizable liquid crystal composition,a content of the polyfunctional polymerizable liquid crystal compoundrepresented by formula (M-1) and (M-2) is preferably from 3% by weightto 60% by weight, and more preferably 5% by weight to 50% by weight.

From the viewpoint of improving hardness, and heat resistance andsolvent resistance, based on a total amount of the polymerizable liquidcrystal compound, it is preferable that the content of a monofunctionalpolymerizable compound (inclusive of monofunctional polymerizable liquidcrystal compound) in the polymerizable liquid crystal composition isless than 5% by weight, more preferably less than 2% by weight, anddesirably close to 0.

In conventional polymerizable liquid crystal composition, themonofunctional polymerizable liquid crystal compound is an essentialcomponent (for example in patent document 12). In comparison, for theliquid crystal composition of the present invention, even if suchcomponent is included, based on a total amount of the polyfunctionalpolymerizable liquid crystal compound, it is included in an amount ofnot more than 5% by weight.

Compound represented by formula (2) as described in Patent Document 12also corresponds to the monofunctional polymerizable liquid crystalcompound.

[3. Solvent]

A solvent of the polymerizable liquid crystal composition is preparedsuch that the coating becomes easy. The solvent of the solution is forexample, ester solvents, amide solvents, alcohol solvents, ethersolvents, glycol monoalkyl ether solvents, aromatic hydrocarbonsolvents, halogenated aromatic hydrocarbon solvents, aliphatichydrocarbon solvents, halogenated aliphatic hydrocarbon solvents,alicyclic hydrocarbon solvents, ketone solvents, acetate solvents anddiacetate solvents, and the like.

Examples of the ester solvents are such as, alkyl acetate, ethyltrifluoroacetate, alkyl propionate, alkyl butyrate, dialkyl malonate,alkyl glycolate, alkyl lactate, monoacetin, γ-butyrolactone andγ-valerolactone, and the like. Alkyl acetate are such as methyl acetate,ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate,3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentylacetate, and the like. Alkyl propionate are such as methyl propionate,methyl 3-methoxypropionate, ethyl propionate, propyl propionate andbutyl propionate, and the like. Alkyl butyrate are such as methylbutyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propylbutyrate, and the like. Dialkyl malonate are such as diethyl malonate,and the like. Alkyl glycolate are such as, methyl glycolate and ethylglycolate, and the like. Alkyl lactate are such as methyl lactate, ethyllactate, isopropyl lactate, n-propyl lactate, butyl lactate andethylhexyl lactate, and the like.

Examples of amide solvents are such as N-methyl-2-pyrrolidone,N,N-dimethylacetamide, N-methyl-propionamide, N,N-dimethylformamide,N,N-diethylformamide, N,N-diethyl acetamide, N,N-dimethylacetamidedimethyl acetal, N-methyl-caprolactam, and dimethyl imidazolidinone, andthe like.

Examples of alcohol solvents are such as methanol, ethanol, 1-propanol,2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol,butanol, 2-ethyl butanol, n-hexanol, n-heptanol, n-octanol, 1-dodecanol,ethylhexanol, 3,5,5-trimethyl hexanol, n-amyl alcohol,hexafluoro-2-propanol, glycerol, ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol, tripropylene glycol, hexylene glycol, 1,3-butanediol,1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol,2,5-hexanediol, 3-methyl-3-methoxy butanol, cyclohexanol and methylcyclohexanol, and the like.

Examples of ether solvents are such as ethylene glycol dimethyl ether,diethylene glycol dimethyl ether, bis(2-propyl) ether, 1,4-dioxane andtetrahydrofuran (THF), and the like.

Examples of glycol monoalkyl ether solvents are such as, ethylene glycolmonoalkyl ethers, diethylene glycol monoalkyl ethers, triethylene glycolmonoalkyl ethers, propylene glycol monoalkyl ether, dipropylene glycolmonoalkyl ethers, ethylene glycol monoalkyl ether acetates, diethyleneglycol monoalkyl ether acetate, triethylene glycol monoalkyl etheracetates, propylene glycol monoalkyl ether acetate, dipropylene glycolmonoalkyl ether acetate, diethylene glycol methyl ethyl ether, and thelike. Ethylene glycol monoalkyl ethers are such as ethylene glycolmonomethyl ether and ethylene glycol monobutyl ether, and the like.Diethylene glycol monoalkyl ethers are such as diethylene glycolmonoethyl ether, and the like. Propylene glycol monoalkyl ethers aresuch as propylene glycol monobutyl ether, and the like. Dipropyleneglycol monoalkyl ethers are such as dipropylene glycol monomethyl ether,and the like. Ethylene glycol monoalkyl ether acetate are such asethylene glycol monobutyl ether acetate, and the like. Diethylene glycolmonoalkyl ether acetate are such as diethylene glycol monoethyl etheracetate, and the like. Propylene glycol monoalkyl ether acetate are suchas propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate and propylene glycol monobutyl ether acetate, and thelike. Dipropylene glycol monoalkyl ether acetate are such as dipropyleneglycol monomethyl ether acetate, and the like.

Examples of aromatic hydrocarbon solvents are such as benzene, toluene,xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene,n-propylbenzene, t-butyl benzene, s-butyl benzene, n-butyl benzene, andtetralin. Preferred examples of halogenated aromatic hydrocarbonsolvents are such as chlorobenzene, and the like. The aliphatichydrocarbon solvents are preferably hexane and heptane, and the like.The halogenated aliphatic hydrocarbon solvents are preferablychloroform, dichloromethane, carbon tetrachloride, dichloroethane,trichlorethylene and tetrachlorethylene, and the like. The alicyclichydrocarbon solvents are such as cyclohexane and decalin, and the like.

Examples of Ketone solvents are such as acetone, methyl ethyl ketone,methyl isobutyl ketone, cyclohexanone, cyclopentanone and methyl propylketone, and the like.

Examples of acetate solvents are such as ethylene glycol monomethylether acetate, propylene glycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, methyl acetoacetate and1-methoxy-2-propyl acetate, and the like.

Examples of diacetate solvents are such as propylene glycol diacetate,1,4-butanediol diacetate and 1,3-butylene glycol diacetate, and thelike.

From the viewpoint of solubility of the liquid crystal compound, the useof amide solvents, aromatic hydrocarbon solvents and ketone solvents arepreferred, and by considering the boiling point of the solvent, thecombined use of ester solvents, alcohol solvents, ether solvents, glycolmonoalkyl ether solvents are also preferred. In the case where plasticsubstrate is used, in order to prevent the corrosion of the plastic,aromatic hydrocarbon solvents, ketone solvents, ester solvents, ethersolvents, alcohol solvents, acetate solvents, glycol monoalkyl ethersolvents are preferred.

From the viewpoint of solubility, based on a total amount of thepolymerizable liquid crystal composition, the solvent of thepolymerizable liquid crystal composition of the present invention ispreferably 40% by weight to 97% by weight, and more preferably 50% byweight to 95% by weight.

The above solvents may be used alone, or may be used in a combination oftwo or more.

[4. Surfactants]

The polymerizable liquid crystal composition of the present inventionmay further comprises surfactants. Due to the effect of improving thesmoothness of the coating film formed from the polymerizable liquidcrystal composition, nonionic surfactants are preferred.

Nonionic surfactants are for example, silicone based nonionicsurfactants, fluorine based nonionic surfactants, hydrocarbon basednonionic surfactants, and the like.

Silicone based nonionic surfactants are for example, by havingnon-modified silicone or modified silicone as the main component, suchas Polyflow ATF-2, Glanol 100, Glanol 115, Glanol 400, Glanol 410,Glanol 435, Glanol 440, Glanol 450, Glanol B-1484, Polyflow KL-250,Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, BYK-300, BYK-302,BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325,BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344, BYK-345,BYK-346, BYK-347, BYK-348, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3500,BYK-3510 and BYK-3570, and the like, manufactured by Kyoeisha ChemicalCo., Ltd.

Fluorine based nonionic surfactants are for example, BYK-340, FTERGENT251, FTERGENT 221MH, FTERGENT 250, FTX-215M, FTX-218M, FTX-233M,FTX-245M, FTX-290M, FTX-209F, FTX-213F, FTERGENT 222F, FTX-233F,FTX-245F, FTX-208G, FTX-218G, FTX-240G, FTX-206D, FTERGENT 212D,FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-720C, FTX-740C, FTX-207S,FTX-211S, FTX-220S, FTX-230S, KB-L82, KB-L85, KB-L97, KB-L109, KB-L110,KB-F2L, KB-F2M, KB-F2S, KB-F3M, and KB-FaM, and the like.

Hydrocarbon based nonionic surfactants are for example, by havingacrylic polymer as the main component such as, Polyflow No. 3, PolyflowNo. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, PolyflowNo. 851-IF, Polyflow No. 90, Polyflow No. 95, Polyflow No. 99C, BYK-350,BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381,BYK-392, and BYK-Silclean3700, and the like.

Furthermore, the surfactant may have a polymerizable functional group inorder for it to be integrated with the polymerizable liquid crystalcompound. The polymerizable functional groups that may be introducedinto the surfactant are such as UV-reactive functional groups andthermal polymerizable functional groups. From the viewpoint of thereactivity with polymerizable liquid crystal compounds, UV-reactivefunctional groups are preferred.

To optimize the wettability of the substrate, surfactants that areclassified as wetting agents may be used in combination. The wettingagents may reduce the surface tension of the polymerizable liquidcrystal composition, and may improve the wettability of the coatedsubstrate. Examples of such wetting agents are such as, the Polyflowseries (KL-100, KL-700, LE-604, LE-605, LE-606), TEGO Twin Series(4000), TEGO Wet Series (KL245, 250, 260, 265, 270, 280, 500, 505, 510),and the like. Furthermore, as an adjuvant of the wetting agent, asurfactant having a fluoride-modified polymer or a fluorine-modifiedacrylic polymer as the main component may also be suitably used. Theseare such as the 3000 series (for example 3277, 3700, 3770, etc.)manufactured by AFCONA Co. Ltd.

It should be noted that both of the above Polyflow and Glanol are theregistered trademark names being used and sold by Kyoeisha Chemical Co.Ltd. BYK is the registered trademark name being used and sold by BYKJapan Co. Ltd. FTERGENT, FTX and KB are the registered trademark namesbeing used and sold by Neos Co. Ltd.

The above surfactant may be used alone, or may be used in a combinationof 2 or more.

[Other Polymerizable Compounds]

Examples of other polymerizable compounds may include compounds that donot have liquid crystallinity such as vinyl derivatives, styrenederivatives, (meth)acrylic acid derivatives, oxirane derivative, oxetanederivatives, sorbic acid derivatives, fumaric acid derivatives anditaconic acid derivatives, and the like. These compounds that do nothave liquid crystallinity are compounds having one polymerizablefunctional group, compounds having two polymerizable functional groupand compounds having three polymerizable functional group.

The other polymerizable compounds may be added as long as it maintains aliquid crystal phase. In view of heat resistance, it is preferable thatthe other polymerizable compounds have a weight ratio of 0.1 or lessrelative to the weight of the polyfunctional polymerizable liquidcrystal compound as in the compounds represented by formula (M-1) and(M-2), and in the case where other liquid crystal compounds and otherpolymerizable liquid crystal compounds are present, it is preferablethat the other polymerizable compounds have a weight ratio of 0.1 orless relative to the total weight of other liquid crystal compounds andother polymerizable liquid crystal compounds with the polyfunctionalpolymerizable liquid crystal compounds such as those represented byformula (M-1) and (M-2). Furthermore, in order to maintain chemicalstrength, it is preferable that two or more polymerizable functionalgroups are present for forming a polymer having three dimensionalstructure.

Examples of monofunctional compounds are such as styrene,nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidenechloride, vinyl pyridine, N-vinylpyrrolidone, vinylsulfonic acid, fattyacid vinyl (e.g. vinyl acetate), a, β-ethylenically unsaturatedcarboxylic acids (e.g. acrylic acid, methacrylic acid, maleic acid,fumaric acid, itaconic acid, etc.), alkyl esters of (meth)acrylic acid(alkyl having 1 to 18 carbons), hydroxyalkyl esters of (meth)acrylicacid (hydroxyalkyl having 1 to 18 carbons), aminoalkyl esters of(meth)acrylic acid (aminoalkyl having 1 to 18 carbons), etheroxygen-containing alkyl ester of (meth)acrylic acid (etheroxygen-containing alkyl having 3 to 18 carbons, e.g. methoxyethyl ester,ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester, ethylcarbylester and butylcarbyl ester), N-vinyl acetamide, p-t-butyl vinylbenzoate, N,N-dimethylamino vinyl benzoate, vinyl benzoate, vinylpivalate, 2,2-dimethyl butanoic acid vinyl ester, 2,2-dimethyl pentanoicacid vinyl ester, 2-methyl-2-butanoic acid vinyl ester, vinylpropionate, vinyl stearate, 2-ethyl-2-methylbutanoic acid vinyl ester,dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl(meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate,dimethyl adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate,dicyclopentenyl (meth)acrylate, 2-acryloyloxyethyl succinate,2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalicacid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid,2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acidphosphate, mono(meth)acrylic acid ester or di(meth)acrylic acid ester ofpolyalkylene glycol having a degree of polymerization of 1-100 such aspolyethylene glycol, polypropylene glycol, and copolymer of ethyleneoxide and propylene oxide, etc., mono(meth)acrylic acid ester ofpolyalkylene glycol having a degree of polymerization of 1-100 such aspolyethylene glycol, polypropylene glycol, and copolymer of ethyleneoxide and propylene oxide, etc. and with terminal capping by an alkylgroup having 1 to 6 carbons, and the like.

Examples of compounds having two polymerizable functional groups aresuch as, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethyloltricyclodecane diacrylate, triethylene glycol diacrylate, dipropyleneglycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycoldiacrylate, bisphenol A EO-added diacrylate, bisphenol A glycidyldiacrylate (Viscoat V #700), polyethylene glycol diacrylate andmethacrylate compounds of the above, and the like.

Examples of compounds having three polymerizable functional groups aresuch as, pentaerythritol tri(meth)acrylate, trimethylolpropanetri(meth)acrylate, trimethylol EO-added tri(meth)acrylate,tris(meth)acryloyloxyethyl phosphate, tris((meth)acryloyloxyethyl)isocyanurate, alkyl-modified dipentaerythritol tri(meth)acrylate,EO-modified trimethylolpropane tri(meth)acrylate, PO-modifiedtrimethylolpropane tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, alkyl-modified dipentaerythritoltetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate,dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritolpenta(meth)acrylate, Viscoat V #802 (number of functional group=8),Viscoat V #1000 (number of functional groups=average of 14). “Viscoat”is a registered trademark name by Osaka Organic Chemical Industry Co.Ltd. Those having functional groups of 16 or more are such as theacrylate compounds obtained by using Boltorn H20 (16 functional groups),Boltorn H30 (32 functional groups), Boltorn H40 (64 functional groups)sold by Perstorp Specialty Chemicals as the raw materials.

In addition, as other polymerizable compounds, polymerizable compoundshaving a bisphenol structure is further included. These compounds aresuitable in assisting uniform alignment and film forming ability ofpolymerizable liquid crystal compounds. Examples of the polymerizablebisphenol derivatives are represented by formula (N-1) to formula (N-6).

The other polymerizable compounds may be used alone, or may be used in acombination of two or more. Furthermore, these compounds may becommercially available products.

[6. Additive]

In order to optimize the polymerization rate, a polymerization initiatormay be added to the polymerizable liquid crystal composition. Thepolymerization initiators are for example, photo-radical initiators.Examples of photo-radical initiators are such as2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173),2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 651),1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Irgacure 127,Irgacure 500 (a mixture of Irgacure 184 and benzophenone), Irgacure2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 754, Irgacure1300, Irgacure 819, Irgacure 1700, Irganox cure 1800, Irgacure 1850,Irgacure 1870, Darocur 4265, Darocur MBF, Darocur TPO, Irgacure 784,Irgacure 754, Irgacure OXE01, Irgacure OXE02, Adeka optomer N-1919,Adeka cruise NCI-831 and Adeka cruise NCI-930, and the like. The above“Darocur” and “Irgacure” are registered trademark names of products soldby BASF Japan Co. Ltd., and the above “Adeka optomer” and “Adeka cruise”are both the registered trademark names of products sold by ADEKA Co.Ltd.

The above photo-radical initiators may further includep-methoxyphenyl-2,4-bis (trichloromethyl) triazine,2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine,9,10-benzphenazine, mixtures of benzophenone/Michler's ketone, mixturesof hexaarylbiimidazole mercaptobenzimidazole,1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl dimethylketal, 2-methyl-1-[4-(methylthio) phenyl]-2-morpholinopropane-1-one,mixtures of 2,4-diethyl xanthone/methyl p-dimethylaminobenzoate, andmixtures of benzophenone/methyl triethanolamine, and the like.

Based on the total amount of the polyfunctional polymerizable liquidcrystal compound, the addition amount of the photo-radical initiatorincluded in the polymerizable liquid crystal composition preferably hasa weight ratio from 0.0001 to 0.20. More preferably, the weight ratio isin the range from 0.001 to 0.15. Even more preferably, the range is from0.01 to 0.15. The above photo-radical initiator may be used alone, ormay be used in a combination of two or more. Furthermore, thesepolymerization imitators may be commercially available products.

Furthermore, these photo-radical polymerization initiators may be usedwith the addition of sensitizers. Examples of sensitizers are such as,isopropylthioxanthone, diethylthioxanthone, ethyl-4-dimethylaminobenzoate (Darocur EDB), 2-ethylhexyl-4-dimethylaminobenzoate (DarocurEHA), and the like. The above sensitizers may be used alone, or may beused in a combination of two or more. Furthermore, these sensitizers maybe commercially available products.

In order to control the polymerization reaction rate and the mechanicalproperties of the polymer, chain transfer agents may be added to thepolymerizable liquid crystal composition. By using the chain transferagents, the reaction rate and chain length of the resulting polymer maybe controlled. By increasing the amount of the chain transfer agent, thepolymerization reaction rate is lowered, and the length of the polymerchain is reduced. The preferred chain transfer agents are thiolcompounds and styrene dimers. The chain transfer agents may be usedalone, or may be used in a combination of two or more. Furthermore,these chain transfer agents may be commercially available products.

The thiol based chain transfer agents are for example, monofunctionalthiols such as dodecanethiol, 2-ethylhexyl-3-mercaptopropionate, and thelike, polyfunctional thiols such as trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate),1,4-bis (3-mercapto butyryloxy) butane (Karenz MT BD 1), pentaerythritoltetrakis (3-mercaptobutyrate) (Karenz MT PE1), and 1,3,5-tris(3-mercapto butyloxyethyl)-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trione(Karenz MT NR1), and the like. The name “Karenz” is a registeredtrademark name from Showa Denko K. K.

The styrene dimer based chain transfer agents are for example,2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-1-butene, and the like.

For the polymerizable liquid crystal composition, it is possible to adda polymerization preventer to prevent the initiation of polymerizationduring storage. Known polymerization preventers may be used, wherein thepreferred examples are such as 2,5-di(t-butyl) hydroxy toluene (BHT),hydroquinone, methylene blue, diphenyl picric acid hydrazide (DPPH),phenothiazine, nitroso compounds such as N, N-dimethyl-4-nitroso anilineand the like, o-hydroxybenzophenone, and benzothiazine derivatives suchas 2H-1,3-benzothiazine-2,4-(3H)-dione, and the like.

In order to improve the storage stability of the polymerizable liquidcrystal composition, it is possible to add a polymerization inhibitor.In the situation where radical occurs in the polymerizable liquidcrystal composition, the polymerization reaction of the polymerizablecompound is promoted. In order to prevent such a situation, it ispreferable that a polymerization inhibitor is added. Polymerizationinhibitors that may be used are such as phenolic antioxidants, sulfurantioxidants and phosphorus acid antioxidants.

In order to improve the weather resistance of the polymerizable liquidcrystal composition, UV absorbers, light stabilizers (radicalscavengers) and antioxidants may be further added.

Examples of UV absorbers are such as, Tinuvin PS, Tinuvin P, Tinuvin99-2, Tinuvin 109, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 328,Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928,Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479,Tinuvin 5236, Adekastab LA-32, Adekastab LA-34, Adekastab LA-36,Adekastab LA-31, Adekastab 1413 and Adekastab LA-51, and the like. Thename “Tinuvin” is a registered trademark name of BASF Japan Co. Ltd,wherein “Adekastab” is a registered trademark name of ADEKA. The UVabsorbers may be used alone, or may be used in a combination of two ormore. Furthermore, these UV absorbers may be commercially availableproducts.

Examples of light stabilizers are such as Tinuvin 111FDL, Tinuvin 123,Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, 5060, Tinuvin5151, Chimassorb 119FL, Chimassorb 944FL, Chimassorb 944LD, AdekastabLA-52, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, AdekastabLA-63P, Adekastab LA-68LD, Adekastab LA-77, Adekastab LA-82, AdekastabLA-87, Cyasorb UV-3346 from Cytek Co. Ltd and Good-rite UV-3034 fromGoodrich Co. Ltd, and the like. The name “Chimassorb” is a registeredtrademark name from BASF Japan Co. Ltd. The light stabilizers may beused alone, or may be used in a combination of two or more. Furthermore,these light stabilizers may be commercially available products.

Examples of antioxidants are such as, Adekastab AO-20, AO-30, AO-40,AO-50, AO-60, AO-80 from ADEKA, Sumilizer BHT, Sumilizer BBM-S,Similizer GA-80 sold by Sumimoto Chemical Co. Ltd., and Irganox 1076,Irganox 1010, Irganox 3114 and Irganox 245 sold by BASF Japan Co. Ltd,and the like. The antioxidants may be used alone, or may be used in acombination of two or more. Furthermore, these antioxidants may becommercially available products.

In order to control the adhesion to the substrate, a silane couplingagent may be added to the polymerizable liquid crystal composition.Examples of silane coupling agents are such as, vinyl trialkoxysilane,3-isocyanate propyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrialkoxysilane, N-(1,3-dimethylbutylidene)-3-(trialkoxysilyl)-1-propanamine, 3-glycidoxypropyltrialkoxysilane, 3-chloro-trialkoxysilane, 3-acryloxy propyltrimethoxysilane, 3-methacryloxypropyl trialkoxysilane, and the like.Furthermore, in the above alkoxysilanes, the silane coupling agent usedmay be a dialkoxysilane where one of the alkoxy groups (out of 3) may besubstituted with a methyl. The above silane coupling agents may be usedalone, or may be used in a combination of two or more. Furthermore,these silane coupling agents may be commercially available products.

[Optical Anisotropical Body]

The present invention also relates to an optical anisotropical bodyformed by the polymerizable liquid crystal composition of the presentinvention. Liquid crystal film is a type of optically anisotropicalbody, and for example, can be obtained by the following steps.

(1) The polymerizable liquid crystal composition or its solution thereofis directly coated onto a supporting substrate in the fluidic state toform a coating film.

(2) The coating film is irradiated with light so as to polymerize thepolymerizable liquid crystal composition, wherein the polymerizableliquid crystal composition in the coating film is formed in a liquidcrystal state and where the alignment is fixed.

The material of the supporting substrate that may possibly be used aresuch as glass and plastic, and the like. Examples of plastics are suchas polyimide, polyamideimide, polyamide, polyetherimide, polyether etherketone, polyether ketone, polyketone sulfide, polyether sulfone,polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethyleneterephthalate, polybutylene terephthalate, polyethylene naphthalate,polyacetal, polycarbonate, polyarylate, acrylic resins, polyvinylalcohol, polypropylene, cellulose, triacetyl cellulose and partiallysaponified product thereof, epoxy resins, phenol resins, and cycloolefinresins, and the like. The supporting substrate is normal sheet shaped orfilm shaped.

Cycloolefin resins are for example, norbornene resins, dicyclopentadieneresins, and the like, but are not limited thereto. Among these, thosehaving no unsaturated bonds, or having unsaturated bonds that arehydrogenated may be suitably used. Examples are such as ring-opened(co)polymer hydrogenated product of 1 or 2 or more kinds of norbornenemonomers, addition (co)polymer of 1 or 2 or more kinds of norbornenemonomers, addition copolymer of norbornene monomer and olefin monomer(ethylene, α-olefin etc.), addition copolymer of norbornene monomer andcycloolefin monomer (cyclopentene, cyclooctene,5,6-dihydro-dicyclopentadiene etc.), and modified products of the above,and the like. More specifically, ZEONEX, XEONOR (co-registeredtrademark, made by Nippon Zeon Co. Ltd), ARTON (registered trademark,made by JSR Co. Ltd.), TOPAS (registered trademark, made by Ticona Co.Ltd.), APEL (registered trademark, made by Mitsui Chemicals Co. Ltd),Esushina (registered trademark, made by Sekisui Chemicals Co. Ltd.) andOPTOREZ (registered trademark, made by Hitachi Chemicals Co. Ltd.) maybe listed.

The film made of plastic (plastic film) used as the supporting substratemay be an uniaxially stretched film or may be a biaxially stretchedfilm. These films for example, may be subjected to hydrophilic treatmentsuch as corona treatment or plasma treatment, and the like, or surfacetreatment such as hydrophobic treatment, and the like. There is noparticular limitation regarding the method of hydrophilic treatment, andfrom the viewpoint of adhesion, corona treatment and plasma treatmentare preferred, and plasma treatment is most preferred. The plasmatreatment reported in the methods disclosed in Japanese Laid OpenPublication No. 2002-226616 and Japanese Laid Open Publication No.2002-121648 may be used. Furthermore, in order to improve the adhesionbetween the liquid crystal film and the plastic film, it is possible toform an anchor coat layer. If such an anchor coat layer is intended forimproving the adhesion of the liquid crystal film and the plastic film,then there is no problem regardless of whether an inorganic material oran organic material is used. Furthermore, the plastic film may be alaminated film. Instead of the plastic film, it is also possible to usemetal substrates such as aluminum, iron and copper etc. with a slit-likegrooves on the surface, or glass substrates such as alkali glass withslit-like etching on the surface, borosilicate glass and flint glassetc.

For these supporting substrates of a glass substrate or a plastic filmand the like, prior to forming a coating film of the polymerizableliquid crystal composition, in the case of forming a liquid crystal filmhaving homogeneous alignment and hybrid alignment, it is possible tofirst perform physical or mechanical surface treatment such as rubbing,and the like. In the case of forming a liquid crystal film withhomeotropic alignment, although surface treatments such as rubbing etc.is generally not carried out, however, to prevent alignment defect andthe like, it is also possible to perform rubbing. Although any methodsmay be employed for rubbing treatment, the methods generally used aresuch as a method where a rubbing cloth made from materials such asrayon, cotton, and polyamide etc. is winded onto a metal roll, whereinthe roll is rotated in motion while being in contact with the supportingsubstrate or the polymeric coating; or a method can be applied where theroll is fixed while moving the supporting substrate, and the like. Therubbing treatment may be directly performed on the supporting substrate,or where the rubbing treatment is performed on a polymeric coating, suchthat the polymeric coating is for instance polyimide, commonly referredto as an alignment film that is coated onto the supporting substrate inadvance. The method of rubbing treatment is as described above.Depending on the type of the supporting substrate, alignment ability mayalso be imparted through inclined vapor deposition of silicon oxide onthe surface.

In the case of the polymerizable liquid crystal composition of thepresent invention, a homeotropic alignment is obtained regardless ofwhether if the above surface treatment is performed or not and whetherif an alignment film is used or not.

For applying the polymerizable liquid crystal composition or a solutionthereof, in order to obtain a uniform film thickness, the coatingmethods used are for example, spin coating method, micro gravure coatingmethod, gravure coating method, wire bar coating method, dip coatingmethod, spray coating method, meniscus coating method and die coatingmethod. In particularly, in methods such as wire bar coating where shearstress is applied when coating the polymerizable liquid crystalcomposition, it is possible to control the alignment of thepolymerizable liquid crystal composition without performing surfacetreatment of the substrate by rubbing.

In the case of applying a solution of the polymerizable liquid crystalcomposition of the present invention, in order to form a polymerizableliquid crystal layer having a homogeneous thickness on the supportingsubstrate after coating, heat treatment may be performed. Heat treatmentfor example can be performed by using a hot plate, a drying oven, or byblowing warm air or hot air, and the like. In the present invention,“polymerizable liquid crystal layer” intends to mean the layers of thepolymerizable liquid crystal composition.

The preferred ranges of the temperature and time for the heat treatmentof the coated film, the wavelength of light used for light irradiation,the amount of light irradiated from a light source etc., may varydepending on the type and composition ratio of the compound used in thepolymerizable liquid crystal composition, whether a photo-polymerizationinitiator is added or not, and the addition amount etc. That is, theconditions of the temperature and time of heat treatment of the coatedfilm, the wavelength of the light used for light irradiation, and theamount of light irradiated from a light source as described below ismerely used to illustrate an approximate range.

The heat treatment of the coated film is preferably carried out underthe conditions where a uniform alignment of the polymerizable liquidcrystal can be obtained. It may be carried out above the liquid crystalphase transition point of the polymerizable liquid crystal composition.An example of the heat treatment method is such as a method where thecoating film is heated to a temperature where the polymerizable liquidcrystal composition exhibits a nematic liquid crystal phase, and whereinthe polymerizable liquid crystal composition in the coating film isformed to have a nematic alignment. In the temperature where thepolymerizable liquid crystal composition exhibits a nematic liquidcrystal phase, it is possible to form a nematic alignment by changingthe temperature of the coating film. In such a method, the coating filmis heated to the high temperature region within the above temperaturerange so that the nematic alignment in the coating film is nearcompletion, and the temperature is lowered such that the alignment canbe further ordered. In the case of any of the heat treatment methodsdescribed above, the heat treatment temperature is from room temperatureto 150° C. From the viewpoint of uniform alignment, the temperaturerange is preferably from room temperature to 120° C., and the range ismore preferably from room temperature to 100° C. The heat treatment timeis from 5 seconds to 2 hours. The time range is preferably from 10seconds to 40 minutes, and the range is more preferably 20 seconds to 20minutes. In order to increase the temperature of the layer composed ofthe polymerizable liquid crystal composition to a predeterminedtemperature, it is preferable that the heat treatment time is 5 secondsor more. In order to prevent low productivity, the heat treatment timeis preferably controlled within 2 hours. In this way, the polymerizableliquid crystal layer can be obtained.

For polymerization through light irradiation, it is possible to fix thealignment state of the polymerizable liquid crystal compound. Thewavelength of light used for light irradiation is not particularlylimited. Electron beam, ultraviolet light, visible light, infrared light(heat wave) etc. may be utilized. From the viewpoint ofpolymerizability, the wavelength range is preferably 150 nm to 500 nm,more preferably 250 nm to 450 nm, and even more preferably 300 nm to 400nm. Examples of the light source are such as, low pressure mercury lamps(germicidal lamp, fluorescent chemical lamp, black light), high pressuredischarge lamps (high pressure mercury lamp, metal halide lamp), shortarc discharge lamps (ultrahigh pressure mercury lamp, xenon lamp,mercury xenon lamp). Preferable examples of the light source are such asmetal halide lamp or xenon lamp, ultra-high pressure mercury lamp andhigh pressure mercury lamp. It is possible to select the wavelengthrange of the irradiated light source by installing filters between thelight source and the polymerizable liquid crystal layer such that only aspecific wavelength range may pass through. The amount of light emittedfrom the light source is at 2 to 5000 mJ/cm² at the time it reaches thecoating film surface. From the viewpoint of polymerizability, the amountof light is preferably in the range from 10 to 3000 mJ/cm², morepreferably in the range from 100 to 2000 mJ/cm². The preferredtemperature at the time of light irradiation is in the same range as theheat treatment described above. Furthermore, the polymerizationenvironment may be possible under any of a nitrogen atmosphere, inertgas atmosphere and air atmosphere. From the viewpoint of improvingcurability, nitrogen atmosphere or inert gas atmosphere is preferred.

The thickness of the optical anisotropical body may be an appropriatethickness based on the retardation and birefringence of the opticalanisotropical body (the value of optical anisotropy).

In general, from the viewpoint of the convenience in design andperformance of the optical element, it is preferably from 0.05 to 100μm, more preferably from 0.1 to 50 μm, and even more preferably from 0.5to 20 μm.

From the viewpoint of the convenience in design and performance of theoptical element, the haze value of the optical anisotropical body ispreferably 1.5% or less, and more preferably 1.0% or less. From theviewpoint of the convenience in design and performance of the opticalelement, the transmittance in the visible light region is preferably 80%or more, and more preferably 90% or more.

The optical anisotropical body obtained by using the polymerizableliquid crystal composition of the present invention is expected to havea low haze value as indicated above.

The optical anisotropical body may also be used as an optical elementthat is integrated with polarizers, and in such situation, it isdisposed at an outer side of the liquid crystal cell. On the other hand,when the optical anisotropical body is an optical compensation element,since there is none or few impurities that is eluted out when liquidcrystals are filled into the cell, it is possible for the body to bedisposed inside the liquid crystal cell. For example, by using themethod disclosed in Japanese Laid Open Publication No. 2008-019434, itis possible to further improve the function of a color filter by forminga polymerizable liquid crystal layer of the present invention on thecolor filter. Furthermore, the type of polarizer used in the opticalelement that can be applied as the optical anisotropical body is notparticularly limited, and besides the widely applied iodine-dopedabsorptive polarizer, the reflective type polarizer of wire gridpolarizer etc. for optical compensation may be suitably used.

EXAMPLES

The following examples are not intended to limit the scope of thepresent invention.

The “glass substrate” refers to the Eagle XG manufactured by CorningInc.

The “polyimide substrate” refers to a polyimide film obtained by coatinga Lixon aligner (trademark) PIA-5370 manufactured by JNC Corporationonto a glass substrate, which is dried at 80° C. for 3 minutes and bakedat 230° C. for 30 minutes.

The “TAC substrate” refers to TACPHAN (trademark), which is a triacetylcellulose film having a thickness of 80 μm.

The “COP substrate” refers to the product obtained by performinghydrophilic treatment on the surface of a ZEONOR (trademark) film/ZEONOR(trademark) 1600R. The ZEONOR (trademark) film/ZEONOR (trademark) 1600Ris a cycloolefin polymer film manufactured by Nippon Zeon Co. Ltd. Thehydrophilic treatment was performed by using an atmospheric pressureplasma surface treatment device (AP-T02-L). For the hydrophilictreatment, besides the methods mentioned in the present disclosure, themethods disclosed in Japanese Laid Open Publication No. 2002-226616 maybe used. The contact angle between the COP substrate and pure water is30° at 25° C. The contact angle was measured by a contact angle meterCA-A manufactured by Kyowa Interface Science Co. Ltd.

[Conformation of Alignment]

The conformation of alignment is performed by the following steps.

-   -   (1) The substrate with an optical anisotropical body is        sandwiched between two crossed nicols disposed polarizers.    -   (2) The substrate was observed from the front direction to        confirm the presence or absence of light leakage. If light        leakage is not visually observed, the alignment of the optical        anisotropical body was judged as “good”. If light leakage is        visually observed, the alignment of the optical anisotropical        body was judged as “poor”.    -   (3) (a) when viewed from the front, besides light leakage, it        displays a dark field view, and (b) when viewed from any of the        top, bottom, left, right directions, it displays a bright field        view, then such optical anisotropical body is judged as having        “homeotropic alignment”.

[Measurement by Using Polarization Analyzer]

Retardation was measured by using OPTIPRO polarization analyzermanufactured by Shintech Inc. A polarized light having a wavelength of550 nm was irradiated on the substrate with an optical anisotropicalbody.

The irradiation angle of the polarized light was measured at 5 degreeincrements. The irradiation angle of the polarized light is from −50degrees to 0 degrees, and from 0 degrees to 50 degrees when the normaldirection of the film surface is 0 degree. The retardation is defined ashaving a relation of Δn×d, wherein Δn represents optical anisotropy andd is the optical path length of the measured light passing through theoptical anisotropical body.

[Evaluation of Heat Resistance]

The evaluation of heat resistance is performed by the following steps.

-   -   (1) The retardation of the substrate with an optical        anisotropical body is measured by the measuring light with        incident angle of +40 degrees, and defined as Re1.    -   (2) The substrate was baked in an oven at 200° C. for 30        minutes.    -   (3) The retardation of the baked substrate with an optical        anisotropical body is measured by the measuring light with        incident angle of +40 degrees, and defined as Re2.

(4) If the Re2/Re1 value is 0.9 or more, then the heat resistance of theoptical anisotropical body is judged as “good”, and if it is less than0.9, then the heat resistance of the optical anisotropical body isjudged as “poor”.

[Film Thickness Measurement]

The film thickness of the optical anisotropical body is measured with afine shape measuring apparatus. The fine shape measuring apparatus isthe Alpha-step IQ from KLA TENCOR Corporation.

The thickness of the optical anisotropical body on the glass substrateis measured by cutting off the glass portion and removing the opticalanisotropical body from the glass substrate with an opticalanisotropical body for measurement.

[Evaluation of Solvent Resistance]

The solvent resistance of the substrate with an optical anisotropicalbody is evaluated by the following steps.

-   -   (1) The substrate with an optical anisotropical body is baked in        an oven at 200° C. for 30 minutes,    -   (2) Next, the thickness of a cured film of the polymerizable        liquid crystal compound of the substrate was measured, and        designated as “thickness before immersion”,    -   (3) Subsequently, the substrate is immersed in an equivalent        amount mixture solution of NMP (N-methyl-2-pyrrolidone) and BC        (ethylene glycol monobutyl ether) at 50° C. for 5 minutes,    -   (4) Next, the thickness of the cured film of the polymerizable        liquid crystal compound of the substrate was measured, and        designated as “thickness after immersion”.

In the case where thickness after immersion/thickness before immersionis 0.9 or more, the solvent resistance is evaluated as “good”, and whenit is below 0.9, the solvent resistance is evaluated as “poor”.

Compound (M-1-1-1) and compound (M-1-1-2) were synthesized by using themethods disclosed in Makromol. Chem., 190, 3201-3215 (1998).

Compound (M-1-7-1) was synthesized by using the same methods disclosedin the WO97/00600 pamphlet.

Compound (M-1-22-1) and compound (M-1-22-2) were synthesized by usingthe methods disclosed in Japanese Laid Open Publication No. 2003-238491.

Compound (M-2-11-1) was synthesized by using the methods disclosed inJapanese Laid Open Publication No. 2008-100982.

Compound (A-3-1) was OGSOL EA-0200 (n1+n2=2), and compound (A-6-1) usesONF-1. Furthermore, GA-1000 (hereinafter referred to as compound(GA-1000)) having a diepoxy acrylate portion was used. These compoundswere produced by Osaka Gas Chemicals.

Compound (A-2-1) manufactured by Changzhou Tronly New ElectronicMaterials Co. Ltd was used.

Compound (M-2-1) was synthesized using the same method disclosed inMacromolecules, 26, 6132-6134 (1993). Compound (M-3-2) was synthesizedby using the method disclosed in Makromol. Chem. 183, 2311-2321 (1982).

[Preparation of Composition 1]

Approximately 10 parts by weight of compound (GA-1000), 45 parts byweight of compound (M-1-1-1), 45 parts by weight of compound (M-1-22-1),5 parts by weight of Irgacure (trademark) 907, 0.25 parts by weight ofBYK-333, 0.1 parts by weight of Irganox 1076 were respectively weighedand mixed with 400 parts by weight of cyclopentane, and the mixture washeated at 40° C. for 1 hour. Thereafter, the mixture was passed througha membrane filter having a pore size of 0.1 μm, and was named ascomposition 1.

[Preparation of Compositions 2 to 13]

Compositions 2 to 13 was obtained through the same preparation processas in composition 1 by mixing the components in the weight ratio shownin Table 1. Except for the drying temperature, the values in Table 1represents the weight ratio of the materials of these compositions.

Example 1

The optical anisotropical body was formed by the following process.

-   -   (1) Composition 1 was spin coated onto the glass substrate at        1000 rpm for 15 seconds,    -   (2) dried at 80° C. for 3 minutes,    -   (3) allowed to stand for 3 minutes at 25° C., 50% rh, to        accomplish example 1.    -   (4) At 25° C., 50% rh, irradiation was performed using        ultra-high pressure mercury lamp with a 365 nm UV light for 5. 6        seconds at 90 mW/cm².

The ultra-high pressure mercury lamp used has a power consumption of 500W as manufactured by Ushio Inc.

The film thickness of the optical anisotropical body is 1.0 μm. Theoptical anisotropical body has good alignment. FIG. 1 shows themeasurement results by using the polarization analyzer device.

Examples 2 to 11, Comparative Examples 1 to 3

Examples 2˜11, examples 18˜20, comparative examples 1˜3 and comparativeexample 6 was prepared in the same manner as in example 1. However, inreplacement of the composition 1 used in process (1) of example 1, aweight ratio shown in Table 1 was used instead. Furthermore, inreplacement of the temperature used in process (2) of example 1, thedrying temperature (T/° C.) shown in Table 1 was used instead.

In Table 1, the solvent resistance, heat resistance and alignment of therespective examples and comparative examples are described. The blankcolumn in Table 1 indicates the relevant sections where confirmation wasnot performed. The optical anisotropical body on the substrate asconfirmed in the present invention all displayed a homeotropicalignment.

TABLE 1 Compar- Compar- ative ative Exam- Exam- Exam- Exam- Exam- Exam-Exam- Exam- Exam- Exam- Exam- ple 7 ple 8 ple 9 ple 1 ple 2 ple 1 ple 2ple 3 ple 4 ple 5 ple 6 Composi- Composi- Composi- Composi- Composi-Composition 1 Composition 2 tion 3 tion 4 tion 5 tion 6 tion 7 Compound10 6 10 0 10 10 10 (GA-1000) Compound 0 0 0 0 0 0 0 (A-3-1) Compound 0 00 0 0 0 0 (A-2-1) Compound 0 0 0 10 0 0 0 (A-6-1) Compound 45 47 0 0 4530 20 (M-1-1-1) Compound 0 47 0 0 0 0 0 (M-1-1-2) Compound 0 0 0 45 0 00 (M-1-7-1) Compound 45 0 45 0 0 30 60 (M-1-22-1) Compound 0 0 45 45 0 00 (M-1-22-2) Compound 0 0 0 0 45 0 0 (M-2-7-1) Compound 0 0 0 0 0 30 0(M-3-1) Compound 0 0 0 0 0 0 20 (M-3-2) Cyclopentanone 400 400 400 400400 400 400 Irgacure-907 5 5 0 5 5 5 5 NCI-930 0 0 5 0 0 0 0Irganox-1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BYK-333 0.25 0 0 0.25 0 0 0TEGO Flow 0 0.25 0.25 0 0.25 0.25 0.25 370 Solvent Good Good Good GoodGood Poor Poor resistance Heat Good Good Good Good Good Poor Poorresistance Substrate Glass Poly- COP TAC Glass Poly- Glass Glass GlassGlass Glass sub- imide sub- sub- sub- imide sub- sub- sub- sub- sub-strate sub- strate strate strate sub- strate strate strate strate stratestrate strate Drying 80 80 80 80 80 80 80 80 80 80 80 temperature (T/°C.) Alignment Good Good Good Good Good Good Good Good Good Good GoodCompar- Compar- ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam-ple 3 ple 10 ple 11 ple 18 ple 19 ple 20 ple 6 Composi- Composi-Composi- Composi- Composi- Composi- Composi- tion 8 tion 9 tion 10 tion11 tion 11 tion 12 tion 13 Compound 0 0 0 10 10 0 10 (GA-1000) Compound0 0 12 0 0 0 0 (A-3-1) Compound 0 10 0 0 0 10 0 (A-2-1) Compound 0 0 0 00 0 0 (A-6-1) Compound 50 0 44 45 45 0 10 (M-1-1-1) Compound 0 45 0 0 045 0 (M-1-1-2) Compound 0 0 0 0 0 0 0 (M-1-7-1) Compound 50 0 44 45 45 060 (M-1-22-1) Compound 0 45 0 0 0 45 0 (M-1-22-2) Compound 0 0 0 0 0 0 0(M-2-7-1) Compound 0 0 0 0 0 0 20 (M-3-1) Compound 0 0 0 0 0 0 0 (M-3-2)Cyclopentanone 400 400 400 400 400 400 400 Irgacure-907 5 0 0 5 5 0 0NCI-930 0 5 5 0 0 5 5 Irganox-1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BYK-333 00 0 0.25 0.25 0 0 TEGO Flow 0.25 0.25 0.25 0 0 0.25 0.25 370 SolventGood Good Good Good Good Poor resistance Heat Good Good Good Good GoodPoor resistance Substrate Glass Glass Glass Glass Glass Glass Glass sub-sub- sub- sub- sub- sub- sub- strate strate strate strate strate stratestrate Drying 80 80 80 60 60 60 60 temperature (T/° C.) Alignment PoorGood Good Good Good Good Good

From the results of the examples and the comparative examples, theoptical anisotropical body obtained by using the polymerizable liquidcrystal composition of the present invention all showed a goodhomeotropic alignment, and further, a good chemical strength isconfirmed.

Composition 31˜40 was prepared in the same manner as in example 1.However, in replacement of the composition 1 used in process (1) ofexample 1, a weight ratio shown in Table 2 was used instead.

TABLE 2 Example 31 Example 32 composi- composi- composi- composi-composi- composi- composi- composi- composi- composi- tion 31 tion 32tion 33 tion 34 tion 35 tion 36 tion 37 tion 38 tion 39 tion 40compound(GA-1000) 10 10 10 10 10 10 10 10 10 10 compound(M-1-1-1) 45 4545 45 45 45 45 45 45 45 compound(M-1-22-1) 39 42 43 43.5 44 40 42 4343.5 44 compound(M-3-1) 6 3 2 1.5 1 0 0 0 0 0 compound(M-3-2) 0 0 0 0 05 3 2 1.5 1 cyclopentanone 400 400 400 400 400 400 400 400 400 400Irgacure-907 0 0 0 0 0 0 0 0 0 0 NCI-930 5 5 5 5 5 5 5 5 5 5Irganox-1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BYK-333 0 0 0 0 00.1 0.1 0.1 0.1 0.1 Tego flow 370 0.25 0.25 0.25 0.25 0.25 0.25 0.250.25 0.25 0.25

FIG. 2 shows a content of compound (M-3-2) versus heat resistance of theoptical anisotropical body corresponding to the compositions 36-40 inExample 32. X-axis of FIG. 2 shows the percentage of a content ofcompound(M-3-2), based on a total amount of the polyfunctionalpolymerizable liquid crystal compound. Y-axis of FIG. 2 shows heatresistance of the optical anisotropical body.

FIG. 3. shows a content of compound (M-3-1) versus heat resistance ofthe optical anisotropical body corresponding to the compositions 31-35in Example 31. X-axis of FIG. 3 shows the percentage of a content ofcompound(M-3-1), based on a total amount of the polyfunctionalpolymerizable liquid crystal compound. Y-axis of FIG. 3 shows heatresistance of the optical anisotropical body.

FIGS. 2 and 3 shows the optical anisotropical body obtained by using thepolymerizable liquid crystal composition. Decreasing compounds (M-3-1)and (M-3-2), being monofunctional polymerizable liquid compound, at twopercentages thereof heat resistance of the optical anisotropical body isdrastically increased. Thus, a content of a monofunctional polymerizableliquid compound is less than 2% by weight, a good chemical strength(heat resistance) is confirmed.

INDUSTRIAL APPLICABILITY

By using the polymerizable liquid crystal composition of the presentinvention, a polymerizable liquid crystal layer that allows formation ofa uniform homeotropic alignment even without forming an alignment filmon the supporting substrate and has excellent heat resistance andsolvent resistance can be made. It is possible to form a liquid crystalfilm from the polymerizable liquid crystal composition, and the liquidcrystal film becomes a material of the optical element including theoptical compensation element.

What is claimed is:
 1. A polymerizable liquid crystal composition,comprising: a polyfunctional polymerizable liquid crystal compound and acardo-type fluorene monomer, wherein based on a total amount of thepolyfunctional polymerizable liquid crystal compound, a content of amonofunctional polymerizable liquid compound is less than 2% by weight.2. The polymerizable liquid crystal composition according to claim 1,wherein the cardo-type fluorene monomer is at least one compoundselected from the group of compounds represented by formula (A-1) to(A-6):

wherein, in formula (A-1), L^(1a) and L^(1b) independently representalkyl having 1 to 4 carbons, R^(1a) and R^(1b) independently representalkylene having 2 to 4 carbons, Z³¹ independently represents hydrogen ormethyl, k1 and k2 independently represent an integer from 0 to 4, m31and n31 independently represent an integer from 0 to 6; in formula(A-2), Z³² independently represents hydrogen or methyl, m32 and n32independently represent an integer from 1 to 3, L^(2a) and L^(2b)independently represent alkyl having 1 to 6 carbon, phenyl or fluorine,j1 and j2 independently represent an integer from 0 to 4; in formula(A-3), Z³³ independently represents hydrogen or methyl, R^(3a) andR^(3b) independently represent hydrogen, methyl or ethyl group, m33 andn33 independently represent an integer from 0 to 3; in formula (A-4),Z³⁴ represents hydrogen or methyl, R^(4a) and R^(4b) independentlyrepresent hydrogen or alkyl having 1 to 6 carbons, m34 and n34independently represent an integer from 0 to 10; in formula (A-5), Z³⁵independently represents hydrogen or methyl; in formula (A-6), Z³⁶independently represents hydrogen or methyl, R^(5a) and R^(5b)independently represent hydrogen or alkyl having 1 to 6 carbons, L^(2a)and L^(2b) independently represent alkyl having 1 to 6 carbons, phenylor fluorine, j1 and j2 independently represent an integer from 0 to 4,m35 and n35 independently represent an integer from 1 to 3, m36 and n36independently represent an integer from 1 to
 3. 3. The polymerizableliquid crystal composition according to claim 2, wherein the cardo-typefluorene monomer is at least one compound selected from the group ofcompounds represented by formula (A-1), formula (A-2), formula (A-3),formula (A-5) and formula (A-6).
 4. The polymerizable liquid crystalcomposition according to claim 1, wherein a polymerizable functionalgroup of the polyfunctional polymerizable liquid crystal compound is a(meth)acryloxy group.
 5. The polymerizable liquid crystal compositionaccording to claim 1, wherein the polyfunctional polymerizable liquidcrystal compound is at least one compound selected from the group ofcompounds represented by formula (M-1) and formula (M-2):

wherein, in formula (M-1) and formula (M-2), A^(M) independentlyrepresents a divalent group selected from 1,4-phenylene,1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl,1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl or fluorene-2,7-diyl, whereinin the divalent group, at least one hydrogen may be substituted byfluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl,difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxyhaving 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkanoylhaving 1 to 5 carbons, Z^(M) independently represents a single bond,—OCH₂—, —CH₂O—, —COO—, —OCO—, —COS—, —SCO—, —OCOO—, —CONH—, —NHCO—,—CF₂O—, —OCF₂—, —CH₂CH₂—, —CF₂CF₂—, —CH═CHCOO—, —OCOCH═CH—, —CH₂CH₂COO—,—OCOCH₂CH₂, —CH═CH—, —N═CH—, —CH═N—, —N═CCH₃—, —CCH₃═N—, —N═N— or —C≡C—,q represents an integer from 1 to 4, c and d independently represents aninteger from 0 to 3, wherein 1≤c+d≤4, a independently represents aninteger from 0 to 20, R^(M) independently represent hydrogen or methyl,Y^(M) independently represent a single bond, —O—, —COO—, —OCO— or—OCOO—, Q represents a single bond, —O—, —COO—, —OCO— or —OCOO—.
 6. Thepolymerizable liquid crystal composition according to claim 1, whereinbased on a total amount of the polymerizable liquid crystal composition,a content of the polyfunctional polymerizable liquid crystal compound isfrom 3% by weight to 60% by weight.
 7. The polymerizable liquid crystalcomposition according to claim 1, wherein based on a total amount of thepolymerizable liquid crystal composition, a content of the cardo-typefluorene monomer is from 0.01% by weight to 15% by weight.
 8. Apolymerizable liquid crystal layer, obtained by applying thepolymerizable liquid crystal composition according to claim 1 directlyonto a support substrate.
 9. The polymerizable liquid crystal layeraccording to claim 8, wherein the support substrate is a glasssubstrate.
 10. The polymerizable liquid crystal layer according to claim8, wherein the support substrate is a glass substrate coated withplastic thin film or a plastic substrate made of plastic film.
 11. Thepolymerizable liquid crystal layer according to claim 10, wherein aplastic of the plastic thin film and the plastic film is at least oneselected from polyimide, polyamide-imide, polyamide, polyether-imide,polyether ether ketone, polyether ketone, polyketone sulfide, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide,polyethylene terephthalate, polybutylene terephthalate, polyethylenenaphthalate, polyacetal, polycarbonate, polyarylate, acrylic resins,polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose,partially saponified product of triacetyl cellulose, epoxy resins,phenolic resins and cycloolefin resins.
 12. The polymerizable liquidcrystal layer according to claim 10, wherein a plastic of the plasticthin film and the plastic film is at least one selected from polyimide,polyvinyl alcohol, triacetyl cellulose, partially saponified product oftriacetyl cellulose, acrylic resins, and cycloolefin resins.
 13. Thepolymerizable liquid crystal layer according to claim 8, wherein thesupport substrate is a glass substrate coated with plastic thin film byrubbing treatment, corona treatment or plasma treatment on the surface,or the support substrate is a plastic substrate made of plastic filmwith rubbing treatment, corona treatment or plasma treatment on thesurface.
 14. The polymerizable liquid crystal layer according to claim8, wherein an alignment state of the polymerizable liquid crystalcomposition is homeotropic alignment.